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Extraordinarily High Pseudocapacitance of Metal

Cite this: DOI: 10.1039/x0xx00000x
Organic Framework Derived Nanostructured Cerium
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Oxide

ChemComm Accepted Manuscript

Received 00th January 2012, Sandipan Maiti, Atin Pramanik and Sourindra Mahanty*
Accepted 00th January 2012

DOI: 10.1039/x0xx00000x

www.rsc.org/

MOF derived CeO2 showed a pseudocapacitance of 1204 Fg -1

at 0.2 Ag-1, far exceeding its theoretical capacitance (560 Fg-
1
). The present study demonstrates that combination of a two-
way strategy, controlled nano-architecture and redox active
electrolyte additive, could potentially alleviate both low
energy density and capacitance fading issues plaguing the
current metal oxide pseducapacitors.

Electrochemical pseudocapacitors (EC), which stores electrical

energy by reversible surface or near-surface redox (Faradaic)
reactions, are the most promising energy storage devices that can
effectively close the power/energy gap between batteries and
conventional dielectric or electrical double layer capacitors.1
Therefore, development of pseudocapacitors with high power
density as well as high energy density is critical to the success of
electric vehicles (EV). Metal oxides, especially RuO2,2 Co3O4,3
NiO,4 and MnO2,5 are considered to be the prime candidates owing
to their high intrinsic capacitance. CeO2, a low cost rare earth metal
oxide with eco-friendly nature and good redox characteristics, is an
attractive alternative material, but not being paid due attention
possibly because of its comparatively lower theoretical capacitance
(560 Fg-1) to that of MnO2 (1109 Fg-1). As a result, only a handful of
studies are devoted to exploit the pseudocapacitive properties of
CeO2.6-9 Wang et al.6 have obtained a capacitance of 278 Fg-1 from
CeO2 nanoparticle /3D graphene composite. A composite of nano
CeO2-activated carbon delivered a capacitance of 162 Fg-1.8
Recently, Padmanathan and Selladurai9 reported a high capacitance
of 644 Fg-1 for carbon supported CeO2 nanorods. As an
electrochemically active material, nanostructure has significant
effect on pseudocapacitance.10 It is well established that surface area Fig.1 (a) FESEM micrograph of Ce-BTC (b) FESEM micrograph of
and morphology are the two most important parameters that guide CeO2 (c) TEM image of CeO2 (d) SAED (e) x-ray diffractogram of
the pseudocapacitive performance of metal oxides. To approach the CeO2 (f) HRTEM image of CeO2
theoretical capacitance in practice, it would be required to utilise the
maximum possible surface along with fast redox kinetics. Metal we report a simple and scalable synthesis of nanostructured CeO2 by
organic frameworks (MOF), constructed by metal ions or clusters using [Ce(1,3,5-BTC)(H2O)6] (1,3,5-BTC = 1,3,5-benzene-
and organic linkers, are compounds that can offer the highest surface tricarboxylate) MOF, henceforth referred as Ce-BTC, as a sacrificial
area. Additionally, presence of nanosized cavities and open channels template. Ce-BTC was synthesized following a solvothermal method
in these materials would allow small molecules to enter and escape, described by Liu et al.12 and characterised by XRD and FITR to
rendering MOFs to behave as ideal sacrificial templates for ascertain its formation (Fig.S1, ESI†). Simply by calcination of Ce-
synthesizing nanomaterials with unique structural features.11 Here, BTC at 650oC for 3 h resulted in straw yellow powder of CeO2 (see

This journal is © The Royal Society of Chemistry 2012 J. Name., 2012, 00, 1-3 | 1
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ChemComm DOI: 10.1039/C4CC05363J
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experimental details and Fig.S2, ESI†). A schematic representation

of formation of Ce-BTC MOF and subsequent CeO2 is given in
Scheme 2, ESI†. When evaluated as electrode material for aqueous
electrochemical supercapacitor, 92% of its theoretical capacitance
could be realised. Recently, we have demonstrated that addition of
K4Fe(CN)6 into KOH significantly influences the pseudocapacitive
performance of MnO2.13 Adopting a similar strategy, a dramatic
improvement for MOF derived CeO2 is found in the present study,
where a pseducapacitance of 1204 Fg-1 could be achieved, far
exceeding its theoretical capacitance (560 Fg-1) (for calculation of
capacitance see 1.4 Experimental, ESI†).
Fig.1a shows the morphology of the synthesized Ce-BTC. Well-
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defined aligned nanobars (length 0.5-1.5 μm and width 50-150 nm)

are formed with sharp edges. It can be discerned from the FESEM
micrograph of CeO2 (Fig.1b) that the original morphology of the

ChemComm Accepted Manuscript

parent Ce-BTC is mimicked; the dimension of the CeO2 nanobars
being (length 0.5-1.0 μm and width 50-100 nm). TEM images
(Fig.1c and Fig.S3c, ESI†) reveal that these nanobars are constructed
of numerous brick-like nanoparticles, assembled in a brick-upon-tile
pattern. This kind of arrangement would generate a large number of
voids resulting in high surface area and would also make the
maximum proportion of the surfaces accessible to the electrolyte
leading to high capacitance. In the selected area diffraction pattern
(Fig.1d), observation of well-defined spots arranged in circular rings
confirms the formation of well-crystallised polycrystalline CeO2
with characteristics planes clearly identified. Phase purity and
crystallinity of the synthesized CeO2 powder were further examined
by the XRD (Fig.1e). All the observed diffraction peaks can be
indexed to cubic phase of CeO2 (space group Fm3m). Rietveld
refinement of the phase provided a good fitting with R profile (Rp),
Rweighted profile (Rwp) and goodness of fit (χ2) values of 14.246%,
19.600%, and 3.5496 respectively. The obtained lattice parameter, a
= 5.4043(3)Å is in excellent agreement with JCPDS data file number
01-078-0694 and also, with the literature values indicating high
purity of the sample.14 The detailed structural data as obtained from
the Rietveld refinement are given in Table-S1, ESI†. Mismatch
between the calculated and experimentally observed peak intensities
for (111) and (200) peaks is indicative of preferred orientation in the
CeO2 crystallites. That the preferred orientation is predominantly
along the (111) and (200) is also reflected in the observed lattice
fringes in the HRTEM image (Fig.1f). The structural features of the
synthesised CeO2 were further probed by Raman spectroscopy
(Fig.S4, ESI†). The observed band at 460 cm-1 in the Raman
spectrum corresponds to F2g symmetry in the cubic phase of CeO2.15
Nitrogen adsorption-desorption isotherms and corresponding pore
size distribution plots for synthesized Ce-BTC and CeO2
demonstrate mesoporous nature (Fig.S5, ESI†). BET surface area
values are calculated to be 27.3 and 77 m2g-1 respectively. The high
surface area of the MOF derived CeO2 presumably resulted from the
unique brick-upon-tile morphology containing a large amount of
voids. Coexistence of a narrow Barrett-Joyner-Halenda (BJH) pore-
size distribution centred at ~3.6 nm (structural pores), a broad pore-
size distribution in the range of 6-11 nm (inter-particle pores) would
enable significant increase in the electrolyte accessibility.
The capacitive charge storage in CeO 2 in aqueous KOH would
involve two simultaneous processes: (i) surface adsorption /
desorption of K+-ions and (ii) intercalation / de-intercalation of
K+-ions into / from the CeO 2 surface and can be represented as
Non-faradic: (CeO2)surface + K+ + e- ↔ (CeO2.K+)surface (1)
Faradic: CeIVO2 + K+ + e- ↔ CeIIIO.OK (2)
In order to evaluate the redox behaviour, CV measurements
were conducted at seven different scan rates ranging from 2
mVs-1 to 100 mVs-1 with cells constructed using CeO 2 as
working electrode, platinum mesh as counter electrode,
Fig.2 (a) & (b) cyclic voltammetry of CeO2 at different scanning rate
in 3 M KOH and in 3 M KOH+ 0.1 M K4Fe(CN)6 (c) & (d)
galvanostatic charge discharge profiles of CeO2 at different current
densities in 3 M KOH and in 3 M KOH+ 0.1 M K4Fe(CN)6
Ag/AgCl as reference electrode and 3 M KOH and 3 M KOH + 0.1
M K4Fe(CN)6 as electrolytes in the potential window of 0.0 to 0.5 V
(Fig.2a and Fig.2b, respectively). The shape of the CV curves clearly
demonstrates typical pseudocapacitive characteristics in both
electrolytes. Appearance of a well-resolved pair of redox peaks at
around 0.23/0.35 V can be attributed to the faradaic redox
conversion of Ce3+Ce4+.7 A near-linear increase in peak current
with increasing scan rate in the peak current vs 1/2 plot (Randles-
Sevcik plot, Fig.S6b, ESI†) is indicative of diffusion controlled
redox processes. From the galvanostatic charge discharge profiles
(Fig.2c), specific capacitance of 502 Fg-1 is obtained in 3 M KOH at
a current density of 0.2 Ag-1. Observance of such high capacitance
(92% of its theoretical value) can be attributed to the unique brick-
upon-tile morphology of the MOF derived CeO2; ion-buffering
reservoirs can be formed in the mesopores minimizing diffusion
paths to the interior surfaces and the mesoporous walls would serve
as low-resistant pathways for easy movement of ions.16 Interestingly,
addition of 0.1 M K4Fe(CN)6 into 3 M KOH electrolyte resulted in a
remarkably high capacitance of 1204 Fg-1 at 0.2 Ag-1 (calculated
from Fig.2d). As pseudocapacitance arises from the surface or near-
surface reversible redox reactions, addition of a complimentary
Fe(CN)64-/Fe(CN)63- redox-active couple to the electrolyte with
matching redox potentials of 0.20/0.37 V (see Fig.S7, ESI†), would
supplement the CeIV/CeIII redox reactions at the electrode/electrolyte
interface by acting as an electron buffer source.13,17 The total pore
volume of CeO2 is found to be 0.217 cm3g-1. Considering that the
Born radius of Fe(CN)64-/Fe(CN)63- being ~0.4 nm, a large number
of the redox additive anions could be accommodated. Further
positive influence of K4Fe(CN)6 redox additive on the reaction
kinetics is demonstrated in Fig.3a. As the current density is
increased, capacitance of CeO2 decreases with or without redox
additive following the common trend for metal oxide
supercapacitors, but the reversibility and sustainability is more
pronounced in case of redox additive with a value of 435 Fg-1 at a
high current density of 10 Ag-1 compared to 205 Fg-1 in KOH only.
The results indicate that conjugation of electrochemically reversible
Fe(CN)64-/Fe(CN)63- couple to quasi-reversible CeIV/CeIII reduces
the ionic diffusion resistance and thereby, enhances the redox
kinetics.

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Fig.3 (a) variation of capacitance with increasing current
density (b) cycling behaviour (c) electrochemical impedance
spectra with zoomed data at the high frequency region in the
inset and (d) Ragone plots of CeO 2 in 3 M KOH and 3 M KOH
+ 0.1 M K4Fe(CN)6
Cycling behavior of these assymmetric cells has been tested in
the potential window of 0.0 to 0.4 V at a constant current
density of 5 Ag-1 for 5000 cycles (Fig.3b). After equilibration in
the first few cycles, a steady capacitance of 580 Fg-1 is obtained
in 3 M KOH + 0.1 M K 4Fe(CN)6 which is much higher than the
capacitance (248 Fg-1) observed in 3 M KOH. In both cases, no
discernable fading occurs highlighting the significant effect of
the brick-upon-tile morphological feature. The electrochemical
response from the CeO 2 electrodes was further examined by
electrochemical impedance spectroscopy. The impedance
spectra (Fig.3c) show typical capacitive behaviour in both
cases. Addition of K 4Fe(CN)6 leads to a slight increase in the
solution resistance (Rs) from 0.90 to 1.03 Ω, but the charge
transfer resistance is low in both cases indicating rapid
diffusion. The sharp line in the low frequency region indicates
the capacitive nature.
Sustainability of high energy density at high power densities is
the key factor for evaluating the performance of a
supercapacitor. On the basis of the galvanostatic charge-
discharge results at different current densities, the energy and
power densities of CeO2 were calculated (Eqns 3 and 4, ESI†)
for both the electrolytes, 3 M KOH and 3 M KOH + 0.1 M
K4Fe(CN)6. From the Ragone plot (Fig.3d), high energy density
is observed for MOF derived CeO 2 in 3 M KOH. The energy
density is further enhanced by addition of 0.1 M K4Fe(CN)6
with very high values of 95.8 and 20.7 Wh kg-1 at power
densities of 150 and 5560 W kg-1. These values are much
superior to those reported previously 6 and also to the current
commercial supercapacitors (3-9 Wh kg-1 at 3000-10000 W kg-
1 13
) validating the effectiveness of the simple strategy adopted in
this work.
In conclusion, it is demonstrated that by using metal organic
framework as an exo-template for synthesizing metal oxides, its
unique morphological features can be mimicked and put to
advantage for electrochemical supercapacitor application.
Further, addition of a fast redox active couple with closely
matched potentials significantly influences the supercapacitive
performance of MOF derived CeO 2 with a remarkably high
value of 1204 Fg-1. A capacitance value of 580 Fg-1 at a high
current density of 5 Ag -1 and excellent stability up to 5000
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DOI: 10.1039/C4CC05363J
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charge-discharge cycles with nearly 100% capacity retention
clearly highlights benefits of the two-way strategy adopted. The
present work may also stimulate the search for other redox
active additive for developing high performance metal oxide
suparcapacitors.
The authors thank Director, CSIR-CGCRI for kind permission
to publish this work. Financial support from CSIR via
TAPSUN NWP0056 project is gratefully acknowledged.
Notes and references
Address: Fuel Cell & Battery Division
CSIR-Central Glass & Ceramic Research Institute
Kolkata 700032 India
and CSIR-Network Institutes for Solar Energy (NISE), India
E-mail: mahanty@cgcri.res.in; s_mahanty@hotmail.com
Tel: +91-33-2322 3495 Fax: +91-33-2473 0957†
ChemComm Accepted Manuscript
Electronic Supplementary Information (ESI) available: [Experimental
details, further additional material and electrochemical characterization
data]. See DOI: 10.1039/c000000x/
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